A wrinkle paint which contains, per 100 parts by weight of a mixture comprising (A) from 40 to 95 parts by weight acrylic resin of hydroxyl group value from 40 to 200, (B) from 5 to 60 parts by weight of low nuclear melamine resin which contains at least 40 wt % of hexakisalkoxymethylmelamine and (C) from 5 to 30 parts by weight of crosslinked type organic resin fine particles of average particle diameter from 0.01 to 10 μm, from 0.1 to 5 parts by weight as sulfonic acid of a sulfonic acid compound which has been blocked with a tertiary amine of boiling point from 80 to 150° C. is known as a paint with which paint films which have a wrinkle pattern can be obtained (see Japanese Examined Patent Publication H3-10671). However, in this case there is a disadvantage in that a stable wrinkle pattern is not obtained in the paint film.
Furthermore, a paint which is characterized in that it contains, per 100 parts by weight in total of (A) from 60 to 95 parts by weight of hydroxyl group containing paint film forming base resin and (B) from 5 to 40 parts by weight of low nuclear methylated melamine resin, (C) from 0.1 to 3 parts by weight as the amount of sulfonic acid of a reaction mixture of 1 equivalent of sulfonic acid and from 1.5 to 30 equivalents of secondary or tertiary amine of boiling point from 30 to 250° C. and (D) from 0.2 to 10 parts by weight of organopolysiloxane which has 2 or more as the total per molecule (blocked)isocyanate groups at the ends of the molecules is known as a paint with which paint films which have a fine wrinkle pattern design can be formed (see Japanese Unexamined Patent Application Laid Open H5-320578). However, in this case the wrinkle pattern design lacks stability with respect to the passage of time and, furthermore, there is a further disadvantage in that a wrinkle pattern design is not obtained in a stable manner due to slight changes in the painting conditions and, moreover, there is yet another problem in that the staining resistance when it is used outdoors is inadequate.
Furthermore, a paint which is characterized in that it contains per 100 parts by weight in total of (A) from 65 to 95 parts by weight of polyether resin which has a hydroxyl group value of from 5 to 110 and (B) from 5 to 35 parts by weight of low nuclear methylated melamine resin, (C) from 0.1 to 3 parts by weight of the sulfonic acid of a reaction mixture of 1 mol of sulfonic acid and at least 7.2 mol of secondary amine, (D) from 1 to 15 parts by weight of fine silica powder of average particle diameter not more than 10 μm and (E) from 1 to 30 parts by weight of one or more type of material selected from among organic resin particles and inorganic glass particles of average particle diameter from 2 to 70 μm and organic resin fibers and inorganic fibers of average diameter from 2 to 50 μm is known as a paint with which paint films which have a wrinkle pattern design which has good corrosion resistance and excellent design potential and pattern stability can be formed (see Japanese Unexamined Patent Application Laid Open H5-039443). However, in this case the mol ratio of secondary amine to sulfonic acid is excessive and so there is a disadvantage in that when an organosilicate-based agent for providing hydrophilicity is combined the hydrophilic performance declines over a short period of time.
Furthermore, a thermosetting resin composition which contains (A) a film-forming polyol resin of which the hydroxyl value is from 5 to 300 mgKOH/g and the number average molecular weight is from 500 to 20,000, (B) a hardening agent which can react with the abovementioned film-forming polyol resin (A), (C) an organosilica sol of particle diameter from 10 to 100 nm and of which degree of hydrophobicity expressed as the hexane tolerance value is at least 15.0 ml and (D) at least one type of material selected from among the partially hydrolyzed condensates of alkoxysilane compounds is known as a thermosetting resin composition with which hardened materials which have excellent staining resistance outdoors are obtained (see Japanese Unexamined Patent Application Laid Open H11-124501). However, in this case there is a disadvantage in that the wrinkle pattern design of the hardened material is not stable even if the hardening agent is a low nuclear melamine resin and an acid catalyst where an aromatic sulfonic acid has been blocked with equimolar amine is used.
The present invention is intended to provide resin compositions which can be used in wrinkle pattern paints with which it is possible to form paint films with which the wrinkle pattern design of the paint film is stable with respect to the passage of time and which, moreover, have excellent paint film staining resistance even in cases where they are used outdoors.